WO2002010507A1

WO2002010507A1 - Process for digesting woodchips and digester additives

Info

Publication number: WO2002010507A1
Application number: PCT/US2001/023766
Authority: WO
Inventors: George K. Wai; Abdul Q. Khan
Original assignee: Ashland Inc.
Priority date: 2000-07-27
Filing date: 2001-07-27
Publication date: 2002-02-07
Also published as: US6551452B2; US6649023B1; CA2417793C; US20020121348A1; AU2001280863A1; CA2417793A1

Abstract

The invention relates to a process for digesting woodchips used in papermaking. The process employs a digester additive, which is a mixture of (a) a polyglycoside, and (b) a polyoxyalkylene glycol. The digester additives are compatible and stable at elevated temperatures in the highly alkaline white liquor used in the digestion of woodchips into pulp. The invention also relates to the digester additive compositions.

Description

PROCESS FOR DIGESTING WOODCHIPS AND DIGESTER ADDITIVES

FIELD OF THE INVENTION

BACKGROUND OF THE INVENTION In the Kraft process for making paper, woodchips are cooked (digested) in a digester at an elevated temperature in white liquor. The white liquor is essentially a caustic solution containing polysulfides. The woodchips swell in the presence of the caustic and the polysulfides penetrate into the capillaries of the wood. This process dissolves the lignin in the woodchips that binds the wood fibers of the wood together. Ideally, all of the woodchips are cooked uniformly during the digestion process. However, in practice, not all of the fibers in woodchips will be separated. Any unseparated particles will be classified as "rejects". If a large quantity of rejects are screened out during this pulping process, "low yield" (defined as dry weight of pulp produced per unit dry weight of wood consumed) will result.

Over the years, anthraquinone (AQ) was and is still successfully used in the pulping industries as a digester additive. AQ enhances the pulping rate, and most importantly, reduces the amount of "rejects" and leads to increases in yield.

However, AQ can be expensive to use and it is relatively insoluble in white liquor, even at an elevated temperature. This insolubility in white liquor creates processing problems, such as pipe and screen plugging, and scaling in the digester. It is also known that the use of AQ detrimentally affects the tall oil by-product recovered during the pulping process.

In order to obviate the problems associated with using AQ, surfactants are added to the white liquor to reduce or eliminate the plugging and scaling problems normally encountered with AQ. In addition, certain surfactants and surfactant mixtures are known to provide wetting properties that allow quick and more uniform penetration of the cooking liquor into the capillaries of woodchips, thus reducing the "rejects" as well as reducing the cooking time. U.S. Patents 4,906,331 and 5,127,993 disclose the use of polyoxyalkylene glycols' (POGs') that can reduce reject and increase yield. However, these POGs (such as PLURONIC® F108 & L-62 polyols) are not compatible in the alkaline white liquors.

U.S. Patents 5,298,120 and 5,501,769 disclose a digester additive that is a diester of the same POGs reacted with oleic acid. The patents indicate that the diester results in improved dispersibility in the white liquor. With heat in alkaline white liquor, the diester will saponify (hydrolyze) back to the original POGs for them to work. Since it takes time for the saponification to occur, these diesters by then is already dispersed in the white liquor resulting in a relatively more uniform cooking of the woodchips in the digester. U.S. Patent 5,250,152 discloses a blend of ethoxylated alcohols and dialkylphenols as digester additives that can increase yields and reduce rejects. U.S. Patents 6,036,817 and 5,728,265 disclose a number of surfactants, including sulfosuccinates, polyglycosides, and poly(methyl-alkylsilicone) as chip penetrating aids. IP Patents 06033386 & 07527528 disclose the use of AQ and surfactants

(including ethoxylate secondary alcohols and alkyphenols blends). WO 9529288 claims AQ treated with rosin with a polyvalent metal and water-soluble surfactant. DE 3905311 discloses AQ with substituted polyglycol ether like alkylphenol or naphthol of a 2-ring aromatic hydroxy compound with 4-20 moles of EO. These inventions emphasize a lower AQ level usage complemented by surfactants in an attempt to reduce the problem of AQ scaling and plugging during pulping.

Ethoxylated alkylpenols, dialkyl phenols, both primary and secondary alcohols, are also documented in many disclosures. However, they are neither soluble nor dispersible in the highly alkaline white liquor rendering them marginally effective. At elevated temperature above 150°C, the solubility of these surfactants worsens. This issue is addressed in U.S. Patents 5,298,120 and 5,501,769 that disclose attempts to disperse the POG uniformly throughout the white liquor by transforming the POGs' into its diester equivalent before use.

SUMMARY OF THE INVENTION The invention relates to a process for digesting woodchips used in papermaking. The process employs digester additives, which are mixtures of (a) a polyglycoside, and (b) a polyoxyalkylene glycol. The mixtures are compatible and stable at elevated temperatures in the highly alkaline white liquor used in the digestion of woodchips into pulp. The invention also relates to the digester additive compositions.

The digester additives are effective in reducing both the Kappa number and percentage of rejects during the cooking of woodchip to pulp. However, unlike most surfactant-based digester additives used commercially, the new digester additives are miscible with and effective with highly alkaline white (cooking) liquors having high solids, especially at temperature >160°C. The use of the digester additives results in the uniform cooking of the woodchips in the digester, improve good yields of woodpulp and a decrease in % of rejects, and a lack of deposits on the digesting equipment that is commonly associated with the use of anthraquinone. The combination of (a) and (b) exhibits unexpected and synergistic benefits.

BEST MODE AND OTHER MODES OF PRACTICING THE INVENTION

The polyglycosides used in the surfactant mixtures include glycosides and glycoside derivatives such as alkyl glycosides, alkoxylated alkyl glycosides, polyglycosides, polyalkylglycosides, alkoxylated polyalkylglycosides, alkylpolysaccharides, and the like. A glycoside is a composition comprised predominantly of an acetal or ketal of a saccharide with an alcohol. Typical saccharides from which the glycoside is derived include glucose, fructose, mannose, galactose, talose, gulose, allose, altrose, idose, arabinose, xylose, lyxose and ribose. The preferred glycosides are glucosides due to the ready availability of glucose as a starting material. The synthesis of polylglycosides is disclosed in U.S. Patents 3,598,865; 3,721,633; 3,772,269; 3,640,998; and 3,839,318, which are hereby incorporated by reference.

Akyl and alkoxy polyglycosides, preferably alkyl polyglycosides for use in the present invention have the formula: R₁O-(glycosyl)x where R_\ is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from about 6 to about 30, preferably from about 8 to about 16, carbon atoms; and x is 1 to 5, preferably from 1 to 4. The glycosyl is preferably a monsaccharide (glucose). To prepare these compounds, the alcohol or alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a source of glucose, to form the glucoside (attachment at the 1 -position). The additional glycosyl units can then be attached between their 1-position and the preceding glycosyl units 2-, 3-, 4- and/or 6-position, preferably predominately the 2-position. Alkylpolysaccharides are disclosed in U.S. Patent 4,565,647. These compositions have a hydrophobic group containing from about 6 to about 30 atoms, preferably from about 10 to about 16 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group containing from about 11/2 to about 10, preferably from about 11/2 to about 3, most preferably from about 1.6 to about 2.7 saccharide units. Any reducing saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties.

Typical hydrophobic groups include alkyl groups, either saturated or unsaturated, branched or unbranched containing from about 6 to about 30, preferably from about 8 to about 16, carbon atoms. Preferably, the alkyl group is a straight chain saturated alkyl group. Suitable alkyl polysaccharides are octyl, nonyldecyl, undecyldodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl, di-, tri-, terra-, penta-, and hexaglucosides, galactosides, lactosides, glucoses, fructosides, fructoses and/or galactoses. The polyoxyalkylene glycols used in the mixture is a nonionic surfactant of a block copolymers of polyethylene oxide (EO) and polypropylene oxide (PO) and are represented by the general formula: HO-(EO)_m-(PO)_n-(EO)_m-OH

where m, which may be the same or different, is a number from 0.5 to 50, preferably 1 to 50, and n is a number from 10 to 100, preferably from 10 to 65.

The block copolymers are generally described in U.S. Patent 2,999,045 and U.S. Patent 4,906,331 , which are incorporated herein by reference. Such block copolymers are available from BASF under the name trademark PLURONIC. Examples include PLURONIC L-44, PLURONIC L-62, PLURONIC L-64, PLURONIC F-68, PLURONIC F-108, and PLURONIC F-127 polyols. The average molecular weight of the preferred polyoxyalkylene polyols is from about 500 to about 30,000.

Particularly preferred are block copolymers having an average molecular weight of about 1,100 to 15,000 having from about 10-80 weight percent polyethylene oxide and from about 90-20 weight percent polypropylene oxide, where said weight percent is based upon the weight of the block copolymer.

The digester additive may also contain anthraquinone (preferably no more than about 1.0 weight percent based upon the weight percent of the pulping woodchips), white liquor, and other additives. White liquor is an aqueous mixture comprising chemicals such as caustic soda, sodium sulfate, sodium carbonate, and sodium sulfide, polysulfides, etc. used in pulping woodchips for papermaking. Examples of pulping woodchips used include hardwood, softwood and their mixtures.

Amounts of Components Generally, the weight ratio of polyglycosides (a) to polyalkylene glycols (b) in the mixture is from 10:90 to 90:10, preferably from 15:85 to 85:15. The amount of digesting aid, which is defined as the mixture of surfactant (a) and (b), used in the digesting process is from 0.05 weight percent to 1.00 weight percent, where said weight percent is based upon the weight of air-dried woodchips used, preferably from 0.125% to 0.25%. ABBREVIATIONS AND DEFINITIONS

The following abbreviations are used in the Examples: AQ = Anthroquinone.

H-Factor a single numerical value for expressing the combined 2 values of digester cooking time and pulping temperature for each cooking cycle. This enables changes to be made

1.0 in the time-temperature cycle while maintaining a constant degree of delignification.

Kappa number a number indicative of the relative bleachability or degree of delignification of pulp. The Kappa number

15 Test is the volume (in milliliters) of 0. IN potassium permanaganate consumed by 1 gram of moisture free pulp. Generally, the higher the Kappa number, the more lignin present in the pulp. The Kappa number generally decreases as the digestion time and/or the

20 alkalinity of the cooking liquor is increased.

% Rejects = the dried weight of unseparated particles that are screened out with industry standard of 0.1 inch slots after that cook.

25

POGs polyoxyalkylene glycol having an average molecular weight of about 1100 to 15,000 and an ethylene oxide to propylene oxide ratio of range from 10% to 80% and sold under the trademark PLURONIC®.

30

PGS Glucopon 425N, an alkyl alkoxylated polyglycoside sold by Henkel. It has excellent wetting properties and is caustic stable.

Yield = the weight of dried pulp produced after digestion of a known weight of dried woodchips and usually expressed as in % yield.

EXAMPLES The examples will illustrate specific embodiments of the invention. These examples along with the written description will enable one skilled in the art to practice the invention. It is contemplated that many other embodiments of the invention will work besides these specifically disclosed. All parts are by weight and all temperatures are in °C unless otherwise specified. The Control contains no additive. The Comparative Examples are designated by letters.

TEST PROCEDURE USED TO EVALUATE DIGESTER ADDITIVES

A mixture of hardwood and softwood woodchips with mill white liquor in a ratio of 1 :4 were added into a laboratory autoclave. The autoclave was sealed and the mixture was heated to a certain H-Factor. H-Factor is a single numerical value for expressing the 2 combined values of digester time and pulping temperature. All comparable tests were conducted using the same H-Factor, i.e. @170°C for the same 2-3 hours, depending by the woodchips type used. The woodchips were deliberately undercooked using the same H-Factor. This was to help in determining the discernible differences after each digestion, especially in % yield, % rejects and Kappa numbers.

Ideally, woodchips should be digested to dissolve most of the lignins to free up the cellulosic fibers but maintain sufficient lignin to provide added strength of the paper produced. An effective pulping aid, it should result a cook that produces high % yield with low % reject and at low or constant Kappa number. The test results are set forth in Table I that follows:

Table I Test Result Summary

The % reject for the Control at 1.44 was high. Although it had a high % yield of 50.72, this high % yield could be explained by the presence of a substantial amount of undissolved lignin still trapped in the handsheet that was prepared after each cook. This was verified by its Kappa number of 45.30. As expected, comparative Example A (anthraquinone or AQ) gave the lowest % reject at 0.24. However, the % yield (45.50) was low and it had a low lignin content, as suggested by the light color pulp, which was consistent with the low Kappa number (32.48). This low yield resulted because most of the lignin in the woodchips, after the cook, was already washed from the pulp. The problem with using the AQ was that it was insoluble in the white liquor, even at higher temperatures.

Comparative Example B (POG, which is PLURONIC L62 polyol) had a high yield and low Kappa number. The low Kappa number demonstrated that POGs are effective pulping aids. However, being insoluble in white liquor, they were not being uniformly dispersed in the white liquor, resulting in high reject rate of 1.52%. Comparative Example C (PGS) indicated that the polyglycoside thought soluble in the white liquor had a high Kappa number of 44.6, and was less effective than POGs. The % of rejects at 1.4 was also high.

¹ High lignin content.

² High lignin content.

¹ The active weight ratio of PGS to POG is 5:1. As Table I shows, Mixture 1, which is within the scope of this invention, was the only digester additive that was soluble in white liquor at room and elevated temperature and provided an acceptable yield. In addition, Mixture 1 provides a high yield and a lower Kappa number than the Control. Mixture 1 also demonstrates the synergistic effect than both PGS and POGs when used alone.

Claims

CLAIMS We claim: 1. A process for digesting woodchips used in papermaking comprising:

adding an effective digesting amount of a digester additive comprising a mixture of (a) a polyglycoside, and (b) a polyoxyalkylene glycol to a mixture comprising pulping woodchips ^• and white liquor, wherein the active weight ratio of (a) to (b) is from 10:90 to 90:10.

2. The process of claim 1 wherein the polyglycoside is an alkyl alkoxy polyglycoside having the following structural formula:

RiO-(glycosyl)_x

where Ri is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from about 6 to about 30; and x is from about 1 to about 10; and glycosyl is a monosaccharide group.

3. The process of claim 1 wherein the polyoxyalkylene glycol has the following structural formula:

HO-(EO)_m-(PO)_n-(EO)_m -OH

where m, which may be the same or different, is a number from 1 to 50 , and n is a number from 10 to 65.

4. The process of claim 1 wherein the amount of digester additive, (a) plus (b), is from about 0.05%o to 1.00%) based upon the weight of the woodchips digested.

5. The process of claim 4 wherein the glycosyl group of the polyglycoside is derived from a monosaccharide.

6. The process of claim 4 wherein the structural formula of the polyglycoside is such that in which the alkyl groups contain from about 8 to about 16 carbon atoms and x is about 1 to 10.

8. The process of claim 1 wherein the active weight ratio of (a) to (b) is from about 10:90 to 90:10.

9. The process of claims 1, 2, 3, 4, 5, 6, 7, or 8 wherein the amount of pulping woodchips used is from 10 to 40 weight percent based on the weight percent of the white liquor.

10. A digester additive comprising:

(a) a polyglycoside, and

(b) a polyoxyalkylene glycol,

wherein the weight ratio of (a) to (b) is from about 10:90 to 90:10.

11. The digester additive of claim 10 wherein the polyglycoside is an alkyl alkoxy polyglycoside having the following structural formula:

RιO-(glycosyl)x

where R\ is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from about 6 to about 30, and x is from about 1 to about 10; and glycosyl is a monosaccharide group and the polyglycoside is an alkyl and alkoxy polyglycoside.

12. The digester additive of claim 11 wherein the polyoxyalkylene glycol has the following structural formula:

HO-(EO)_m-(PE)_n-(EO)_m-OH

where m, which may be the same or different, is a number from 1 to 50, and n is a number from 10 to 65.

13. The digester additive of claim 12 wherein the ratio of m to n is about 10 to 90.

14. The digester additive of claim 13 wherein the glycosyl group of the polyglycoside is derived from monosaccharide.

15. The digester additive of claim 14 wherein the structural formula of the polyglycoside is such that in which the alkyl groups contain from about 8 to about 16 carbon atoms; x is about 1 to about 10.

16. The digester additive of claim 15 wherein the weight ratio of (a) to (b) is from about 10:90 to 90:10.